Process of manufacturing liquid hydrocarbons



J. R. Rosa sept. 19,y 1939.

PROCESS v0l' IANUFACTURING LIQUID HYDROGARBONS Filed April e, 1938 mums... znnuipu mCSEkd f mi. ..N

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' INVENToR BYM ATTORNEYS.

Patented Sept. `19, 1939 Paocltss` or MANUFACTURING LIQUID maooARBoNs JamesB. Bose, Edgeworth, Pa'.

Application April 6, 1938, Serial No. 200,359

, '4 Claims'.

This invention relates to a process for converting normally gaseous hydrocarbon material into normally liquid hydrocarbon material, and has particular reference to the treatment of petroleum reiinery gases for the conversion of the same into liquid hydrocarbon materialv in the nature of motor fuel.

As is well known by those acquainted with this art, the gases resulting from the cracking of oil contain saturates and unsaturates, the proportions of which vary in accordance with the variation in the particular fields from which the crude oils are obtained that are subjected to cracking operations.

'15 It is tlie general purpose and object of my invention to provide a process whereby a higher proportion of the saturates and unsaturates in the aforesaid gases may be converted into liquid hydrocarbon than has hitherto been found possible of accomplishment. In the practice of my process, I make use of a catalyst for the purpose of condensing and polymerizing the gaseous hydrocarbons subjected thereto. While my process is of value, irrespective oi the particular kind of catalyst employed, I have found that I am able to eii'ect a maximum recovery of liquid hydrocarbon'sby the use in such process of the particular catalyst set forth herein.

My process is realizable in and through the use of the apparatus illustrated in the drawing,

wherein the ligure is a .flow diagram illustrating my preferred apparatus and showing the relation of the various parts of such apparatus to one another.

Describing my process in connection with the' aforesaid drawing, I denotes a pipe for conducting raw refinery gas to the meter 2, whence it is delivered into a compressor 3, where it -is subjected to a pressure of from 100 to 600 pounds 0 per square inch and whence it is delivered-to a condenser 4, including a water coil 6. By this treatment. hydrocarbons as heavy as butane, together with small amounts of normally liquid hydrocarbons that are heavier than butane, `are condensed and delivered through a pipe 6 into the stabilizer tower 1 having a steam coil 8 in the bottom thereof which is heated to a temperature of approximately 300 F. and which serves to boil oil? the lighter products, which contact 00 with the condenser 8 at the top of the stabilizer.

'Ihis condenser serves to re-condense any 'of the heavier hydrocarbons that are being` carried off by the lighter products, and these heavier hydrocarbons drop to the bottom of the tower, whence they are drawn off` into the cooler I0, to- 5 gether with the liquid which has remained in the bottom of the stabilizer. The cooler is provided with the cooling coil II,` andthe cooled liquid is delivered therefrom into the final-products receiver I2. 10

The gases from the condenser 4 are delivered through pipes I3 and I5 to a recycling meter I6, the pressure of the gases so delivered being suitably reduced by passing through the valve I3-. The gases from the stabilizer 1 are de- 15 livered through pipes I4 and I5 tothe re-cycling meter I6, the pressure of these gases being suitably reduced by passing through the valve 14%'.

It is preferred that the gases delivered to theV re-cycling meter shall have a pressure not in E0 excess of 5 lbs. per square inch. From the recycling meter, the gases are conducted through the pipe I1 to the holder I8.

The gaseous mixturel in the holder I8 isidelivered thence to a compressor I0, where it is 25 subjected to a pressure of from 800 to 1500 pounds `per square inch and is delivered thence under such pressure into the cooler 20. lBy this treatment, the gases are practically completely liquefied, and the liquid, or largely liquid, product is $0 delivered into the liquid holder 2|, under the same pressure. The small proportion of unliqueied gases remaining after this treatment may be taken from the top of the holder through a pipe 22 and used for any desired purpose, such 35 as for heating a stove 23 having therein cracking coils 24 to which the liquid from the holder 2I is conducted through pipe 25. In this stove, the liquid delivered from the holder 2 I is cracked into agaseous condition under temperatures of from 800 to 1500 F. The gaseous uid produced in the cracking coils is delivered through banks of tubular catalyst receptacles 26, 21 and 28, the banks being4 connected by pipes 29 and 30. It win be noted that the cracked product is caused 45 to traverse the full length of the banks of catalyst tubes in series, passing from the bottoms of the tubes 28 in the first bank to the bottoms of the tubes 21 in the second bank and from the tops ct the tubes 21 into the tops of the tubes 2a in 60 vforni of gases and to be carried leads from the top the third bank. The catalyst which I use in the banks of the tubular receptacles 26, 21 and 28 consists preferably of a mixture of carnotite, phosphate rock, Floridan clay, zinc phosphate and barium chloride, bonded together with commercial re bond. 'I'he ingredients are preferably mixed in the follow' g proportions by weight:

Parts Carnotite 27 Phosphate rock 27 Floridan clay 27 Zinc phosphatp 5 Barium chlorirlaa .4. vFire bond l 10.-

It will be noted that the catalyst receptacles are contained in a chamber forming an extension of the stove proper, whereby they will be heated eiiiciently by the products of combustion delivered into the top vof the chamber wherein they are located, the products passing oft` from the bottom of the chamber into a. stack 3|. By this arrangement', the temperature of the cracked product will not be materially reduced when delivered into the pipe or pipes 30, since the exothermicA reaction occurring within the catalyst lreceptacles compensates for the reduction in temperature of the products of combustion passing in contact therewith.

In passing through the catalyst tubes or receptacles, the cracked product is polymerized and converted almost entirely into a hydrocarbon suitable for motor fuel. This hydrocarbon at this stage is in a vaporous condition, and is delivered through one or more pipes 38 into the header 32. From this'header, the polymerized material passes through a pipe 33 having an expansion valve 34, which reduces its pressure to approximately 100 lbs. per square inch, being delivered from said valve to a receptacle 35 having a water coil 36 therein, the purpose ofthe receptacle and coil being to prevent the freezing of the expanding fluid directed through the valve 34. 'I'he fluid from the receptacle 35 is delivered into the ballast chamber or collector 31`. From the ballast chamber 31, the material is delivered in turn to the separator 38, which is provided with a. pipe 38l for draining water therefrom, and thence through the pipe 39, valve 40 and cooler 4|, into the receiver separator 42. The ballast chamber 31, the separator 38 and the receiver separator 42 all cooperate to stabilize the product, enabling material therein which is of an intermediate nature between the liquid and the gaseous state (such as heavy vapors or globules of liquid) to coalesce and unite with the body of the liquid, the latter two receptacles serving the purpose of enabling the lighter products to boil off in the off .by their respective vent lines.

The` lighter products in 38 are conducted through the pipe 43, pressure reducing valve 44, and ilow`meter 45 into the vent line 46 which i of the receiver separator 42 and conveys the gases from the separators 38 and 42 to the re-cycling meter I 6, the pipe 48 being also provided with a pressure reducing valve 468 `by which the pressure oi' the gases from the separators 38 and 42 will be reduced to a pressure preferably not. exceeding 5 lbs. before passing through the re-cycling meter.

The liquid hydrocarbon collected within the receiver separator is delivered through the pipe 41 and valve 48 into the stabilizer 1, where it is subjected to the same treatment as the butane and/or other heavy hydrocarbons delivered from the condenser 4,`the liquid hydrocarbons from both sources being heated by the steam coil 8. The stabilizer 1 thus serves not only to stabilize the liquid hydrocarbons delivered there'into from both sources, but also toblend the same.

It will be noted that, in the practice of my process, I effect the removal of butane and/or other heavier hydrocarbons (such as pentane and pentene) by pressure and condensation,

without recourse to catalyzation; also that the gases from the condenser 4, stabilizer 1, and the stabilizing receptacles 31, 38 and 42 are liquefied by pressure and cooling, the liquid thus produced being cracked under high pressure and this product being largely converted into liquid hydrocarbon by polymerization in the catalyst tubes or receptacles 26, 21 and 28 and by stabilization in the receptacles 31, 38, 42 and 1.

Having thus described my invention, what I claim is:

l. The process of manufacturing liquid hydrocarbons suitable formotor fuel from petroleum refinery gases containing saturates and unsaturates which comprises subjecting the -said gaseous material to a pressure of from 100 to 600 lbs. per square inch and to a cooling action, thereby to condense from such gaseous material hydrocarbons as heavy as and heavier than butane; subjecting the gaseous residue to a pressure of from 800 to 1500 lbs. per square inch and to a cooling action, thereby to liquefy the said residue; subjecting the residue while under the said pressure to a cracking temperature of from 800 to 1500 F.; subjecting the resultant material while under the said pressure to a catalyst to facilitate the polymerization thereof, thereby to form normally liquid hydrocarbon material, said catalyst comprising a mixture of the following ingredients l2. The process of manufacturing liquid hydrocarbons suitable for motor fuel from petroleum refinery gases containing saturates and unsaturates which comprises subjecting the said gaseous material to a pressure of from 100 to 600 lbs. per square inch and to a cooling action, thereby to condense from such gaseous material hydrocarbons as heavy as and heavier than butane; subjecting the gaseousresidue to a pressure of from 800 to 1500 lbs. per square inch and to a cooling action, thereby to liquefy the said residue; subjecting the residue While under the said pressuretoacrackingtemperatureof from 800 to 1500o F.; subjecting the resultant material while under the said pressure and temperature to a catalyst to facilitate the polymerization thereof, thereby to form normally liquid hydrocarbon material, said catalyst comprising a mixture of the following ingredients in approximately the following proportions:

Fire bondV 'andere' L;

and separating normally gaseous materiaifrom said liquid hydrocarbon.

3. The process of manufacturing liquid hydrocarbons suitable for motor fuel from petroleum refinery gases containing saturates and unsaturates which comprises subjecting the said gases to a pressure of from 800 to 1500 lbs. per square inch and to a cooling action, thereby to liquefy the said gases; subjecting the resultant liquid while under the said pressure to a cracking temperature of from 800 to l500 F.; subjecting the resultant material while under the said pressure to a catalyst to facilitate the polymerization thereof, thereby to form normallyvliquid hydro,-

4. The process-of manufacturing liquid hydrocarbons suitabley for motor fuel from petroleum refinery gases containing saturates and unsatu rates which comprisessubjecting the said gases to a pressure of from 800 to 1500 lbs. per square inch and to a cooling action, thereby to liquefy the said gases; subjecting the lresultant liquid while under the said pressure to a cracking temperature of from 800 to 1500 F.; subjecting the resultant material while under the said pressure and temperature to a catalyst to facilitate the polymerization thereof, thereby to form normally liquid hydrocarbon material, said catalyst comprising a mixture of the following-ingredients in` y approximately the following proportions:

, Parts Carnotite l Phosphate rock Floridan clay 2'7 Zinc phosphate l 5 Barium chloride 4 Fire hond Y 10 and separating n'ormally gaseousmaterial from said liquid hydrocarbon.

f JAMES a. Rosa... 25 

